High activity catalyst for hydrosilylation reactions and methods of making the same

ABSTRACT

A heterogeneous catalyst comprising a metal-containing polymer matrix covalently bonded to a support material and a method of making and using such catalysts. The metal-containing polymer matrix comprises metal nano-particles encapsulated in a polymer matrix, e.g., a siloxane. In one aspect, the metal-containing polymer matrix can be bonded to the support material via a hydrophobic group attached to the support material. The catalyst can be recovered after being used in a metal catalyzed reaction and exhibit excellent catalytic activity upon reuse in subsequent reactions.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 61/625,320 entitled “High Activity Catalyst ForHydrosilylation Reactions And Methods Of Making The Same” filed on Apr.17, 2012 which is hereby incorporated in its entirety by reference.

FIELD

The present invention provides heterogeneous catalyst materials suitablefor use in catalyzing a variety of reactions including, for example,hydrosilylation reactions. In particular, the present invention providesmetal catalyst compositions containing metal nanoparticles such as, forexample, platinum nanoparticles. More specifically, the presentinvention provides metal nanoparticles encapsulated in a polymer matrix,which metal-containing matrix is bonded to a support material.

BACKGROUND

Heterogeneous catalysts have advantages over homogenous catalystsincluding the ability to recycle and reuse the catalyst, and the absenceof the active catalyst species in the reaction products. Usually, aheterogeneous catalyst consists of catalytically active particlesdeposited on support particles that are catalytically inactive (e.g.,silica, alumina, etc.). In a few cases, the support particles arethemselves catalytically active. The catalytically active particles aredeposited onto the support by techniques such as impregnation of thecatalytic particles, adsorption of catalyst species from a solution,homogeneous deposition precipitation onto a support, and chemical vapordeposition. The catalytic activity of the heterogeneous catalystsgenerally depends upon factors such as specific surface area, porestructure of the support particles, and the size of the active particleson the support. While these factors may be adjusted to try and increasecatalytic activity, the catalytic activity of heterogeneous catalysts isusually lower than that of homogeneous catalysts, on a weight basis.

One attempt to increase catalyst activity has involved reducing the sizeof the active particles to nanoscale dimensions. Due to this, supportednano Pt catalysts in particular have gained tremendous attraction. Thenano size of the Pt metal increases intrinsic catalytic activity throughan increase in the surface to volume ratio and the specific surfacearea. (See U.S. Pat. No. 7,053,021.) Many of the existing methods forsynthesizing supported nanoparticulate Pt catalysts, however, are thesame as those used for synthesizing normal supported catalysts, i.e.,impregnation, adsorption, homogeneous deposition, and chemical vapordeposition. In all of these, only physical interactions (Van der Waalsforces, e.g.) exist between the catalytically active particles and thesupport. The physical interactions may not be strong enough to withstandthe shear conditions in stirred or fixed bed reactors, especially forcatalytically active particles of nano-size. Such catalysts arevulnerable to loss of the catalytically active particles to the reactionmedium. This could significantly limit their recycle/reuse potential.

U.S. Patent Publication No. 2004/0087441A1 describes PtRu nanoparticlesdirectly applied to the support by reducing precursor metal salts anddepositing the nanoparticles on the support during synthesis. It may benoted that in such a catalyst the attractive forces between the activenanoparticles and the support are physical forces, and this may notprovide sufficiently strong binding between the two. Such catalysts arelikely to be vulnerable to nanoparticle loss in the high shearconditions of fixed bed and stirred reactors.

Other attempts to improve catalytic activity have involved adjusting thecrystal structure, softness, etc., of the nanoparticles. For example,U.S. Pat. No. 6,177,585 describes the use of bi-metallic catalysts,although the catalyst particles are not in the nano size range.

One issue in prior catalyst systems is stabilization of the particlesbecause the nanoparticles tend to aggregate in the absence ofstabilizing agents. Traditionally, nanoparticle stabilization isachieved by using surfactants. Stabilization provided by surfactants isconsidered to be of an electrostatic nature. Steric stabilization ofparticles may be accomplished by encapsulating the nanoparticles in acrosslinked siloxane polymer as described in B.P.S. Chauhan et. al,Journal of Organometallic Chemistry, 686(1-2), p. 24-31, 2003. Suchnanoparticles are reported to be catalytically active, capable of beingseparated from the product liquid by ultracentrifugation, and reused.However, ultracentrifugation is not a cost-effective method ofseparating the nanoparticles for industrial scale processes.

SUMMARY

The present invention provides a nanoparticle heterogeneous metalcatalyst and methods for making such catalysts. In one embodiment, thecatalysts possess high catalytic activity. In one embodiment, thecatalysts are reusable and exhibit excellent stability and activity uponreuse. The catalysts can also be recovered via simple filtrationtechniques and do not require the use of expensive separation columns.

In one aspect, the present invention stabilizes metal particlessterically through encapsulation in a cross linked siloxane polymericmatrix, and simultaneously anchors the cross linked siloxane polymer tosilica particles via covalent bonding linkages. These particles can beeasily separated by filtration, which is a more cost-effective means ofrecovering the catalyst for industrial scale processes.

In one aspect, the present invention provides heterogeneous catalystcomprising a metal-containing polymer matrix covalently bonded to asupport material.

In one embodiment, the metal-containing polymer matrix comprises metalnanoparticles encapsulated in a polymer matrix chosen from an organicpolymer matrix or a siloxane polymer matrix.

In one embodiment, the polymer matrix comprises an organic polymermatrix comprising a polymer or copolymer of a vinyl aromatic, a vinylhalide, an alpha monoolefin, an acrylonitrile, an acrylate, an amide, anacrylamide, an ester, or a combination of two or more thereof.

In one embodiment, the polymer matrix is derived from a siliconhydride-containing polyorganohydrosiloxane of the general formula:

M¹ _(a)M² _(b)D¹ _(c)D² _(d)T¹ _(e)T² _(f)Q_(j)

wherein: M¹=R¹R²R³SiO_(1/2); M²=R⁴R⁵R⁶SiO_(1/2); D¹=R⁷R⁸SiO_(2/2);D²=R⁹R¹⁰SiO_(2/2); T¹=R¹¹SiO_(3/2); T²=R¹²SiO_(3/2); Q=SiO_(4/2); R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are aliphatic,aromatic or fluoro monovalent hydrocarbon having from 1 to 60 carbonatoms; at least one of R⁴, R⁹, R¹² is hydrogen; and the subscript a, b,c, d, e, f, and j are zero or positive subject to the followinglimitations: 2≦a+b+c+d+e+f+j≦6000, and b+d+f>0.

In one embodiment, the polymer matrix comprises a functional groupchosen from a hydride; a carboxyl group, an alkoxy functional group, anepoxy functional group, a triaz-1-yn-2-ium functional group, ananhydride group, a mercapto group, an acrylate, an alkyl, an olefinic, adienyl, or a combination of two or more thereof.

In one embodiment, the polymer matrix comprises a functional groupchosen from —S_(i)—H; —Si(CH₂)_(n)COOR¹³, —Si(CH₂)nSi(OR¹⁴)₃,—Si(OR¹⁵)₁₋₃, —S_(i)(CH₂)_(n)-epoxy, —Si—(CH₂)_(n)—N—N≡N, etc. whereR¹³, R¹⁴, and R¹⁵ is chosen from hydrogen, hydrocarbyl, substitutedhydrocarbyl, or a combination of two or more thereof, and n is chosenfrom 1 to 26.

In one embodiment, the polymer matrix comprises a polysiloxane. In oneembodiment, the polysiloxane is formed from a hydrosiloxane and a vinylsilicon compound.

In one embodiment, the metal nanoparticles are chosen from nanoparticlesof aluminum, iron, silver, zinc, gold, copper, cobalt, nickel, platinum,manganese, rhodium, ruthenium, palladium, titanium, vanadium, chromium,molybdenum, cadmium, mercury, calcium, zirconium, iridium, cerium,oxides and sulfides of such metal, or combinations of two or morethereof.

In one embodiment, the metal-containing polymer matrix has a ratio ofpolymer to metal of from about 1:1000 to about 100:1; from about 1:1 toabout 20:1; from about 10:1 to about 20:1; even from about 12:1 to about16:1.

In one embodiment, the metal particles have a particle size of fromabout 1 to about 100 nanometers.

In one embodiment, the support material is chosen from silicon, asilicate such as a sodium silicate, a borosilicate, or a calciumaluminum silicates, clay, silicate, silica, starch, carbon, alumina,titania, calcium carbonate, barium carbonate, zirconia, metal oxide,carbon nanotubes, synthetic and natural zeolites, polymeric resins inbead or fibrous form, or and mixtures of two or more thereof.

In one embodiment, the metal loading ranges from about 0.001 to 20percent by weight of the support material; from about 0.05 to about 5percent by weight of the support material; even from about 0.1 to about1 percent by weight of the support material.

In one embodiment, the support material comprises a functional groupchosen from a group such as silanol, alkoxy, acetoxy, silazane,oximino-functional silyl group, hydroxyl, acyloxy, ketoximino, amine,aminoxy, alkylamide, hydrogen, allyl, an aliphatic olefinic group, aryl,hydrosulfide, or a combination of two or more thereof.

In one embodiment, the support material comprises a functional groupchosen from —Si—CH═CH₂, —Si—OH, —Si—(CH₂)_(n)C≡CH, —Si—(CH₂)_(n)—NH₂,—Si—(CH₂)_(n)—OH, —Si—(CH₂)_(n)—SH, or a combination of two or morethereof, and n is 1-26, 1-10, even 1-8.

In one embodiment, the metal-containing polymer matrix is covalentlybonded to the support material via a hydrophobic functional groupattached to the support material. In one embodiment, the hydrophobicgroup is chosen from an alkyldisilazane, a vinyl-containing silazane, ora combination thereof.

In one aspect, the present invention provides a metal catalyzed reactionemploying a catalyst in accordance with the present invention includingaspects and embodiments of such catalysts described above and in thedetailed description. In one embodiment, the reaction is chosen from ahydrosilylation reaction, a hydroxylation reaction, a silaesterificationreaction, a hydrogenation reaction, a oxidation reaction, a Heck andSuzuki coupling reaction, a dehydrocoupling reaction.

In another aspect, the present invention provides a method ofsynthesizing supported nanosized metal catalysts, the method comprising(a) forming a metal-containing polymer matrix comprising metalnanoparticles encapsulated in a polymer matrix; and (b) attaching themetal-containing polymer matrix to a support material via covalentchemical bonds.

The method of claim 22 wherein forming the metal-containing polymermatrix comprises forming a colloidal suspension of metal nano-particlesby reacting metal complexes with a silicon hydride-containingpolyorganohydrosiloxane solution in suitable solvent under nitrogenatmosphere, and encapsulating the metal nano-particles in a siloxanematrix.

In one embodiment, the metal complex is selected from a metal saltchosen from PtCl₂, H₂PtCl₆, Pt₂(dba)₃, Pt₂(dvs)₃, Pt(OAc)₂Pt(acac)₂,Na₂PtCl₆, K₂PtCl₆, platinum carbonate, platinum nitrate,1,5-cycooctadienedimethylplatinum(II), platinum perchlorate, aminecomplexes of the platinum ammonium hexachloropalladate(IV),palladium(II) chloride, AuCl₃, Au₂O₃, NaAuO₂, AgCl, AgNO₃, CuSO₄, CuO,Cu(NO₃)₂, CuCl₂, Ru₂O₃, RuCl₂, FeCl₂.6H₂O, ZnCl₂, CoCl₂.6H₂O,NiCl₂.6H₂O, MnCl₂.4H₂O, TiCl₄, vanadium chloride, cadmium chloride,calcium chloride, zirconium tetrachloride, mercuric chloride complexes,or a combination of two or more thereof.

In one embodiment, the silicon hydride-containingpolyorganohydrosiloxane is of the general formula:

M¹ _(a)M² _(b)D¹ _(c)D² _(d)T¹ _(e)T² _(f)Q_(j)

wherein: M¹=R¹R²R³SiO_(1/2); M²=R⁴R⁵R⁶SiO_(1/2); D¹=R⁷R⁸SiO_(2/2);D²=R⁹R¹⁰SiO_(2/2); T¹=R¹¹SiO_(3/2); T²=R¹²SiO_(3/2); Q=SiO_(4/2); R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are aliphatic,aromatic or fluoro monovalent hydrocarbon having from 1 to 60 carbonatoms; at least one of R⁴, R⁹, R¹² is hydrogen; and the subscript a, b,c, d, e, f, and j are zero or positive subject to the followinglimitations: 2≦a+b+c+d+e+f+j≦6000, and b+d+f>0.

In one embodiment, encapsulating the metal nano-particles in thesiloxane matrix comprises exposing the colloidal suspension to thepresence of oxygen for a time period of from about 10 to about 30minutes.

In one embodiment, the method comprises an optional step of removing atleast about 50% of the solvent from the colloidal solution.

In one embodiment, the ratio of polymer to metal complex ranges fromabout 0.001 to about 100.

In one embodiment, the molecular weight of the polysiloxanes range from100 to 50000, and the Si—H content of the polysiloxanes ranges from0.001 to 99 mole percent.

In one embodiment, the nanoparticles are chosen from at least one ofaluminum, iron, silver, zinc, gold, copper, cobalt, nickel, platinum,manganese, rhodium, ruthenium, palladium, titanium, vanadium, chromium,molybdenum, cadmium, mercury, calcium, zirconium, iridium, cerium,oxides and sulfides thereof.

In one embodiment, the polymer matrix comprises a functional groupchosen from a hydride; a carboxyl group, an alkoxy functional group, anepoxy functional group, a triaz-1-yn-2-ium functional group, ananhydride group, a mercapto group, an acrylate, an alkyl, or acombination of two or more thereof.

In one embodiment, the polymer matrix comprises a functional groupchosen from —S_(i)—H; —Si(CH₂)_(n)COOR¹³, —Si(CH₂)nSi(OR¹⁴)₃,—Si(OR¹⁵)₁₋₃, —S_(i)(CH₂)_(n)-epoxy, —Si—(CH₂)_(n)—N—N≡N, etc. whereR¹³, R¹⁴, and R¹⁵ is chosen from hydrogen, hydrocarbyl, substitutedhydrocarbyl, or a combination of two or more thereof, and n is chosenfrom 1 to 26.

In one embodiment, the support material is chosen from silicon, asilicate such as sodium silicate, a borosilicate, or a calcium aluminumsilicate, clay, silica, starch, carbon, alumina, titania, calciumcarbonate, barium carbonate, zirconia, metal oxide, carbon nanotubes,synthetic and natural zeolites, polymeric resins in bead or fibrousform, or a mixture of two or more thereof.

In one embodiment, the reaction is carried out at a temperature betweenabout 5 degree C. to about 150 degree C., and at a pressure ranging from0.001 bar to 10 bar.

In one embodiment, the nanoparticles have a size in the range of fromabout 1 to about 100 nanometers.

In one embodiment, the reaction is carried out in the presence orabsence of suitable solvents.

In one embodiment, the method further comprises drying the supportednanoparticle catalysts

In one embodiment, the support material comprises particles having asize in the range from 50 to 1000 micrometers.

In one embodiment, the ratio of metal loading to support material rangesfrom about 0.001 to 20 percent by weight.

In one embodiment, the support material comprises a functional groupchosen from a group such as silanol, alkoxy, acetoxy, silazane,oximino-functional silyl group, hydroxyl, acyloxy, ketoximino, amine,aminoxy, alkylamide, hydrogen, allyl, an aliphatic olefinic group, aryl,hydrosulfide, or a combination of two or more thereof.

In one embodiment, the support material comprises a functional groupchosen from —Si—CH═CH₂, —Si—OH, —Si—(CH₂)_(n)C≡CH, —Si—(CH₂)_(n)—NH₂,—Si—(CH₂)_(n)—OH, —Si—(CH₂)_(n)—SH, or a combination of two or morethereof, and n is 1-26, 1-10, even 1-8.

In one embodiment, the support material is functionalized with ahydrophobic group.

In one embodiment, the hydrophobic group is chosen from analkyldisilazane, a vinyl-containing silazane, trimethyl disilazane,tetramethyl disilazane, pentamethyl disilazane, hexamethyl disilazane,octamethyl trisilazane, hexamethylcyclo trisilazane,tetraethyltetramethylcyclo tetrasilazane, tetraphenyldimethyldisilazane, dipropyltetramethyl disilazane, dibutyltetramethyldisilazance, dihexyltetramethyl disilazane, dioctyltetramethyldisilazane, diphenyltetramethyl disilazane, octamethylcyclotetrasilazane, vinyltriacetoxysilane and vinyltrialkoxysilanes, or acombination of two or more thereof.

In still another aspect, the present invention provides a processcomprising: (a) conducting a metal catalyzed reaction with a catalystcomprising a metal-containing polymer matrix covalently bonded to asupport material; (b) recovering the catalyst; and (c) conducting asubsequent metal catalyzed reaction with the recovered catalyst.

In one embodiment, the metal catalyzed reaction is chosen fromhydrosilylation, hydroxylation, silaesterification, hydrogenation,oxidation, Heck and Suzuki coupling, dehydrocoupling. In one embodiment,the metal catalyzed reaction comprise a hydrosilylation reactioncomprising reacting a silicon hydride with an unsaturated reactant.

In one embodiment, the silicon hydride is selected from a groupdescribed by (a) the formula

M¹ _(a)M² _(b)D¹ _(c)D² _(d)T¹ _(e)T² _(f)Q_(j)

wherein: M¹=R¹R²R³SiO_(1/2); M²=R⁴R⁵R⁶SiO_(1/2); D¹=R⁷R⁸SiO_(2/2);D²=R⁹R¹⁰SiO_(2/2); T¹=R¹¹SiO_(3/2); T²=R¹²SiO_(3/2); Q=SiO_(4/2); R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are aliphatic,aromatic or fluoro monovalent hydrocarbon having from 1 to 60 carbonatoms; at least one of R⁴, R⁹, R¹² is hydrogen; and the subscript a, b,c, d, e, f, and j are zero or positive subject to the followinglimitations: 2≦a+b+c+d+e+f+j≦6000, and b+d+f>0, or (b) a monomer havinga general formula R′_(m)H_(n)SiX_(4-m-n), where each R′ is independentlyselected from the group consisting of alkyls comprising one to 20 carbonatoms, cycloalkyls comprising four to 12 carbon atoms, and aryls; m=0 to3, n=1 to 3, and m+n=1 to 4; each X is independently selected from a OR′group or a halide. In one embodiment, the silicon hydride is chosen fromtrimethylsilane, dimethylsilane, triethylsilane, dichlorosilane,trichlorosilane, methyldichlorosilane, dimethylchlorosilane,ethyldichlorosilane, cyclopentlydichlorosilane,methylphenylchlorosilane, (3,3,3-trifluoropropyl),heptamethyltrisiloxane hydride, triethoxysilane, trimethoxysilane,hydrogen terminated polydimethylsiloxane, monochlorosilane, or acombination of two or more thereof.

In one embodiment, the unsaturated reactant is selected from the groupconsisting of a hydrocarbon compound or an unsaturated polyether.

In one embodiment, the hydrocarbon compound is described by one or moreof the formulas (CH₂═CH(CH₂)_(g))_(h)R′_(i)Si(OR′)_(4-h-i) and(CH₂═CH(CH₂)_(g)R′_(i)SiCl_(4-h-i), where R′ is independently selectedfrom the group consisting of alkyls comprising one to 20 carbon atoms,cycloalkyls comprising four to 12 carbon atoms, and aryls; g is 0 to 20,h is 1 to 3, I is 0-3, and h+i is 1 to 4.

In one embodiment, the hydrocarbon compounds is chosen from 1-hexene and1-5 hexadiene, trans-2hexene, styrene, allylmethoxytriglycol,alpha-methylstyrene, eugenol, 1-octene, allyl glycidylether,trivinylcyclohexane, allylmethacrylate, allylamine, trichloroethylene,allyl and vinyl ethers, dichlorostyrene, or a combination of two or morethereof.

In one embodiment, the unsaturated polyether is chosen from a blocked orrandom polyoxyalkylenes having at least one of the general formulas:

R¹(OCH₂CH₂)_(z)(OCH₂CH[R³])_(w)OR²  (X);

R²O(CH[R³]CH₂O)_(w)(CH₂CH₂O)_(z)CR⁴ ₂C≡CCR⁴ ₂(OCH₂CH₂)_(z)(OCH₂CH[R³])wR²  (Y);

or

H₂C═CCH₂[R⁴](OCH₂CH₂)_(z)(OCH₂CH[R³])_(w)CH²[R⁴]C═CH₂  (Z)

where R¹ denotes an unsaturated organic group containing from 3 to 10carbon atoms; R² is hydrogen, or a polyether capping group of from 1 to8 carbon atoms chosen from an alkyl group, an acyl group, or atrialkylsilyl group; R³ and R⁴ are monovalent hydrocarbon groups chosenfrom a C₁-C₂₀ alkyl group, an aryl group, an alkaryl group, or acycloalkyl group; R⁴ can also be hydrogen; z is 0 to 100 inclusive and wis 0 to 100 inclusive, with the proviso that z+w>0.

In one embodiment, the process comprises repeating steps (b) and (c) twoor more times. In one embodiment, the process comprises repeating steps(b) and (c) five times.

In one embodiment, the recovered catalyst has a catalytic activitysubstantially similar to activity of the catalyst in step (a). In oneembodiment, the recovered catalyst has a catalytic activity that is atleast 85% of the catalytic activity of the catalyst in step (a). In oneembodiment, the recovered catalyst has a catalytic activity that is atleast 95% of the catalytic activity of the catalyst in step (a). In oneembodiment, the recovered catalyst has a catalytic activity that is atleast 99% of the catalytic activity of the catalyst in step (a).

In one embodiment, the reaction is carried out in a batch, semi batch,or continuous mode at a temperature between about 0 degree C. to 500degree C. and a pressure ranging from 0.01 bar to 100 bar.

In one embodiment, recovering the catalyst is accomplished byfiltration.

These and other aspects and embodiments of the invention are furtherunderstood with reference to the drawings and detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic illustration of metal catalysts in accordance withaspects of the invention and a scheme for forming the same;

FIGS. 2 a and 2 b shows TEM images of Pt nanoparticles supported onsilica. FIG. 2 a shows a magnification of 135,000; FIG. 2 b shows amagnification of 650,000.

FIG. 3 is a solid state ²⁹Si NMR spectrum of a metal catalyst inaccordance with one embodiment of the invention; and

FIG. 4 is an FTIR spectrum of a metal catalyst in accordance with oneembodiment of the invention.

DETAILED DESCRIPTION

The present invention provides a heterogeneous metal catalyst comprisingmetal nanoparticles. In one embodiment, a heterogeneous metal catalystmaterial comprises a metal-containing polymer matrix bonded to a supportmaterial. The metal-containing polymer matrix comprises a polymer matrixhaving a plurality of metal nanoparticles disposed in the polymermatrix. The support material comprises a substrate having functionalgroups at or near the substrates surface that are capable of bondingwith the metal-containing polymer matrix material.

Metal-Containing Polymer Matrix

The metal-containing polymer matrix comprises a polymer matrixcomprising a plurality of metal nanoparticles dispersed in the polymermatrix. In one embodiment, the metal nanoparticles are encapsulated inthe polymer matrix. The polymer matrix may be selected as desired for aparticular purpose or intended use. For example, the polymer matrix maybe chosen to provide a particular functionality for bonding with thesubstrate material or based on the environment in which the catalystwill be used.

In one embodiment, the polymer matrix can comprise an organic syntheticpolymer material. Suitable organic synthetic polymer materials include,but are not limited to thermoplastic polymers, thermoplastic elastomers,etc. Suitable organic polymer materials can include polymers orcopolymers of vinyl aromatic monomers, such as styrene; vinyl halidesuch as vinyl chloride; acrylonitrile; alpha-monoolefins such asethylene, propylene, etc.; acrylates; acrylamides; amides; esters; etc.,or a combination of two or more thereof.

In one embodiment, the polymer matrix comprises a cross linkedpolysiloxane network. The polysiloxane network can comprise acrosslinked or partially crosslinked network of hydrosiloxanes orhydride fluid with a vinyl silicon compound. In one embodiment, thehydrosiloxanes are polyorganohydrosiloxanes comprising a silicon hydride(Si—H) group. In one embodiment, the polyorganohydrosiloxane is ofFormula (1):

M¹ _(a)M² _(b)D¹ _(c)D² _(d)T¹ _(e)T² _(f)Q_(j).  (1)

wherein: M¹=R¹R²R³SiO_(1/2); M²=R⁴R⁵R⁶SiO_(1/2); D¹=R⁷R⁸SiO_(2/2);D²=R⁹R¹⁰SiO_(2/2); T¹=R¹¹SiO_(3/2); T²=R¹²SiO_(3/2); Q=SiO_(4/2); R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independentlyaliphatic, aromatic, cycloaliphatic, or fluoro monovalent hydrocarbonhaving from 1 to 60 carbon atoms, and at least one of R⁴, R⁹, and R¹² ishydrogen. Examples of useful aliphatic groups include, but are notlimited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl,tert-butyl, n-pentyl, iso-pentyl, neopentyl and tert-pentyl; hexyl, suchas the n-hexyl group; heptyl, such as the n-heptyl group; octyl, such asthe n-octyl, isooctyl groups, and the 2,2,4-trimethylpentyl group;nonyl, such as the n-nonyl group; decyl, such as the n-decyl group;cycloalkyl radicals, such as cyclopentyl, cyclohexyl and cycloheptylradicals and methylcyclohexyl radicals. Examples of suitable aryl groupsinclude, but are not limited to, phenyl, naphthyl; o-, m- and p-tolyl,xylyl, ethylphenyl, and benzyl. R⁴, R⁹, R¹² are independently selectedfrom hydrogen. The subscripts a, b, c, d, e, f, and j are zero orpositive subject to the following limitations: 2≦a+b+c+d+e+f+j≦6000,b+d+f>0. The Si—H content of the polysiloxanes can range from 0.001 to99 mole percent.

The polysiloxane can comprise a variety of functionalities to allow themetal-containing polymer matrix to be bonded or adhered to the supportmaterial. Examples of suitable functional groups include, but are notlimited to, hydride functionalities (—S_(i)H); carboxyl functionalgroups, alkoxy functional groups, epoxy functional groups, atriaz-1-yn-2-ium functional group, an anhydride group, a mercapto group,an acrylate, an alkyl, olefinic, dienyl, etc. or a combination of two ormore thereof. Non-limiting examples of suitable functional groupsinclude —S_(i)—H; —Si(CH₂)_(n)COOR¹³, —Si(CH₂)nSi(OR¹⁴)₁₋₃,—S_(i)(CH₂)_(n)-epoxy, —Si—(CH₂)_(n)—N—N≡N, etc. where R¹³, R¹⁴, and R¹⁵can be hydrogen, hydrocarbyl, substituted hydrocarbyl, or a combinationof two or more thereof, and n can be 1 to 26, 2 to 10, even 2 to 8.

In one embodiment, the polymer matrix comprises a polyalkylhydrosiloxane, a polyaryl hydrosiloxane, or a combination of two or morethereof. In one embodiment, the polymer matrix comprises a hydrosiloxanechosen from poly(methyl hydrosiloxane) (PMHS), poly(ethylhydrosiloxane), poly(propyl hydrosiloxane), polyaryl hydrosiloxane(e.g., poly(phenyl hydrosiloxane), poly(tolyl hydrosiloxane)),poly(phenyl dimethylhydrosiloxy)siloxane, poly(dimethyl siloxaneco-methyl hydrosiloxane), poly(methyl hydrosiloxane co-phenyl methylsiloxane), poly(methyl hydrosiloxane coalkyl methyl siloxane),poly(methyl hydrosiloxane co-diphenyl siloxane), poly(methylhydrosiloxane co-phenyl methyl siloxane). The hydrosiloxane can be ahomopolymer or a copolymer comprising two or more hydrosiloxanes.

The vinyl silicon compound is not particularly limited and can be, forexample, a cyclic vinyl siloxane, a non-cyclic vinyl siloxane etc.Examples of suitable vinyl siloxanes includes, but are not limited to,1,3-divinyl-1,1,3,3-tetramethyl disoloxane, 1,3,5trimethyl-1,3,5-trivinyl-cyclotrisiloxane,1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, etc.

The molecular weight of the polysiloxanes of the present invention canrange from 150 to 50000, 200 to 30000, 250 to 25000, 300 to 15000, even500 to 10000. Here as elsewhere in the specification and claims,numerical values can be combined to form new and non-disclosed ranges.It will be appreciated that the polysiloxane network may have someresidual hydride bonds.

The metal nanoparticle material is not particularly limited and can bechosen as desired for a particular purpose or intended use. Themetal-containing polymer matrix comprises nanoparticles chosen fromnanoparticles of aluminum, iron, silver, zinc, gold, copper, cobalt,nickel, platinum, manganese, rhodium, ruthenium, palladium, titanium,vanadium, chromium, molybdenum, cadmium, mercury, calcium, zirconium,iridium, cerium, oxides and sulfides of such metals, or a combination oftwo or more nanoparticles thereof. In one embodiment, the nanoparticlescomprise alloys of two or more metals. In one embodiment, the metalnanoparticles comprise platinum.

In one embodiment, the metal nanoparticles have a particle size of fromabout 1 to about 100 nanometers (nm). In another embodiment, the metalnanoparticles have a particle size of from about 5 to about 90nanometers. In still another embodiment, the metal nanoparticles have aparticle size of from about 10 to about 80 nanometers. In yet anotherembodiment, the metal nanoparticles have a particle size of from about20 to about 70 nanometers (nm). In an even further embodiment, the metalnanoparticles have a particle size of from about 30 to about 60nanometers (nm). In yet a further embodiment, the metal nanoparticleshave a particle size of from about 35 to about 50 nanometers (nm). Hereas elsewhere in the specification and claims, numerical values may becombined to form new or undisclosed ranges. The particle size of themetal nanoparticles may be determined by any suitable method. In oneembodiment, particle size is determined by transmission electronmicroscopy (TEM).

In one embodiment, the weight ratio of polymer to metal is from about1:1000 to about 100:1. In another embodiment, the ratio of polymer tometal is from about 1:100 to about 100:1. In another embodiment, theratio of polymer to metal is from about 1:50 to about 50:1. In anotherembodiment, the ratio of polymer to metal is from about 1:10 to about50:1. In another embodiment, the ratio of polymer to metal is from about1:1 to about 35:1. In another embodiment, the ratio of polymer to metalis from about 1:1 to about 20:1. In another embodiment, the ratio ofpolymer to metal is from about 10:1 to about 20:1. In anotherembodiment, the ratio of polymer to metal is from about 12:1 to about16:1. In one embodiment, the ratio of polymer to metal is about 15:1.Here as elsewhere in the specification and claims, numerical values maybe combined to form new or nondisclosed ranges.

Synthesis of Metal-Containing Polymer Matrix

The metal-containing polymer matrix may be formed by reducing a metalcomplex in solution to form metal nanoparticles, metal oxidenanoparticles, or metal sulfide nanoparticles. In one embodiment, thesolution for reducing the metal complex also serves as the polymermaterial for forming the polymer matrix. In one embodiment, the solutionfor reducing the metal complex is a silicon hydride containingpolyorganohydrosiloxane. Non-limiting examples of suitablepolyorganohydrosiloxane materials can be those described above.

In one embodiment, the method for forming the metal-containing polymermatrix comprises reacting a metal complex with a silicon hydridecontaining polyorganohydrosiloxane solution in a suitable solvent toform a colloidal suspension of metal nanoparticles and subsequentlyreacting the suspension to form a polymer matrix. The reaction may becarried out in an inert atmosphere, such as under a nitrogen atmosphere,to form the metal nanoparticles. In one embodiment, the reaction to formthe metal nanoparticles is carried out at a temperature of about 80° C.Following formation of the nanoparticles, the suspension is subjected toan oxygen environment to effect polymerization and encapsulate the metalnanoparticles. The reaction in the presence of oxygen can be carried outfor a period of from about 5 to about 40 minutes, in one embodiment fromabout 10 to about 30 minutes, in another embodiment, from about 15 toabout 25 minutes.

The method can also comprise removing an amount of solvent from thecolloidal suspension prior to the polymerization/encapsulation reaction.In one embodiment, at least about 50% of the initial solvent content isremoved; in another embodiment at least about 60% of the initial solventcontent is removed; in another embodiment, at least about 70% of theinitial solvent content is removed; in another embodiment, at leastabout 80% of the initial solvent content is removed. In one embodiment,about 50% to about 100% of the initial solvent content is removed; inanother embodiment about 60% to about 100% of the initial solventcontent is removed; in another embodiment, about 70% to about 100% ofthe initial solvent content is removed; in another embodiment about 80%to about 100% of the initial solvent content is removed

The metal complex for forming the metal nanoparticles can be a metalcompound suitable for providing the desired metal. The metal complex canbe a metal compound comprising a metal chosen from aluminum, iron,silver, zinc, gold, copper, cobalt, nickel, platinum, manganese,rhodium, ruthenium, palladium, titanium, vanadium, chromium, molybdenum,cadmium, mercury, calcium, zirconium, iridium, cerium, or a combinationof two or more thereof. Examples of suitable metal complexes for formingmetal nanoparticles include, but are not limited to, PtCl₂, H₂PtCl₆,Pt₂(dba)₃, Pt₂(dvs)₃, Pt(OAc)₂Pt(acac)₂, Na₂PtCl₆, K₂PtCl₆, platinumcarbonate, platinum nitrate, 1,5-cyclooctadienedimethylplatinum(II),platinum perchlorate, amine complexes of the platinum, ammoniumhexachloropalladate(IV), palladium(II) chloride, AuCl₃, Au₂O₃, NaAuO₂,AgCl, AgNO₃, CuSO₄, CuO, Cu(NO₃)₂, CuCl₂, Ru₂O₃, RuCl₂, FeCl₂.6H₂O,ZnCl₂, CoCl₂.6H₂O, NiCl₂.6H₂O, MnCl₂.4H₂O, TiCl₄, vanadium chloride,cadmium chloride, calcium chloride, zirconium tetrachloride, mercuricchloride complexes. As used herein, “dba” refers todibenzylideneacetone, “dvs” refers to divinyl tetramethyl disiloxane,“OAc” refers to acetate anion, and “acac” refers to acetylacetoneligand.

Support Material

The support material can be selected as desired for a particular purposeor intended use. In one embodiment, the support material can be organicpolymer material, an inorganic material, etc. Examples of suitablesupport materials include, but are not limited to, silicon, silicatessuch as sodium silicates, borosilicates or calcium aluminum silicates,different types of clay, silica, starch, carbon, alumina, titania,calcium carbonate, barium carbonate, zirconia, metal oxide carbon,nanotubes, synthetic and natural zeolites, polymeric resins in bead orfibrous form, or mixtures of two or more thereof. Examples of suitableorganic materials include, polymers containing unsaturated functionalgroups such as styrene or vinyl containing compounds. Other examples ofsuitable organic resins include sulfonate resins such as Nafion® resinavailable from DuPont.

The support material can generally be provided as particles. In oneembodiment, the support particles have a particle size of from about 50to about 1000 micrometers. In one embodiment, the support particles havea particle size of from about 100 to about 800 micrometers. In oneembodiment, the support particles have a particle size of from about 200to about 700 micrometers. In one embodiment, the support particles havea particle size of from about 300 to about 600 micrometers. Here aselsewhere in the specification and claims, numerical values may becombined to form new or nondisclosed ranges. The particle size of thesupport particles may be determined by any suitable method. In oneembodiment, particle size is determined by scanning electron microscopy(SEM).

The support material comprises a functional group attached thereto thatis capable of reacting with a moiety of the polymer matrix such that themetal-containing polymer matrix is chemically bonded to the supportmaterial. It will be appreciated that the functional group can beprovided by the natural surface characteristics of the particles (e.g.,surface OH groups on silica) or the particles may be functionalized witha selected moiety to provide a desired reactive site or reactivity. Inone embodiment, where the polymer matrix contains a hydrosilane (SiH)moiety, the support material can be functionalized with any group thatcan react with the SiH moiety such as, for example, via ahydrosilylation reaction, a condensation reaction, etc. In oneembodiment, the support material can be modified with a compoundcomprising a functional group chosen from a group such as silanol,alkoxy, acetoxy, silazane, oximino-functional silyl group, hydroxyl,acyloxy, ketoximino, amine, aminoxy, alkylamide, hydrogen, allyl orother aliphatic olefinic group, aryl, hydrosulfide, a combination of twoor more thereof etc. Silanol, alkoxy, and acetoxy groups are all capableof condensing with Si—H groups. In one embodiment, the support materialcomprises a functional group having an unsaturated carbon-carbon bond(e.g., a double bond or a triple bond). In one embodiment, the supportmaterial has a functional group chosen from —Si—CH═CH₂, —Si—OH,—Si—(CH₂)_(n)C≡CH, —Si—(CH₂)_(n)—NH₂, —Si—(CH₂)_(n)—OH,—Si—(CH₂)_(n)—SH, a combination of two or more thereof, etc, and n 1-26,1-10, even 1-8. The functional groups provided on the support materialcan be chosen as desired to facilitate bonding with the functionalgroups provided on the polymer matrix of the metal-containing matrixmaterial to bond or anchor the metal-containing polymer matrix to thesupport.

In the case of silica support particles and a metal-containing polymermatrix comprising a hydrosiloxane polymer, the inventors have found thatit may be beneficial to functionalize the silica particles with ahydrophobic group to facilitate reaction with the hydrophobic siloxanepolymer. In the present invention, this specific functionalizationprocess (i.e., treating the material with a hydrophobic group) isreferred to as “capping.”

In one embodiment, the substrate particle is functionalized with asilazane. The silazane compound is a generic name of a compound having aSi—N bond in its molecule. Suitable silazanes include, but are notlimited to, disilazanes such as alkyldisilazanes. Specific examples ofsuitable silazanes include, but are not limited to, dimethyl disilazane,trimethyl disilazane, tetramethyl disilazane, pentamethyl disilazane,hexamethyl disilazane (HMDZ), octamethyl trisilazane, hexamethylcyclotrisilazane, tetraethyltetramethylcyclo tetrasilazane,tetraphenyldimethyl disilazane, dipropyltetramethyl disilazane,dibutyltetramethyl disilazane, dihexyltetramethyl disilazane,dioctyltetramethyl disilazane, diphenyl tetramethyl disilazane, andoctamethylcyclo tetrasilazane. In addition, a fluorine-containingorganic silazane compound obtained by substituting a silazane compoundpartially with fluorine may be used. In still other embodiments, thesilazane compounds comprise carbon-carbon double bonds such as, forexample, vinyl groups. An example of a suitable vinyl-containingsilazane is divinyltetramethylsilazane (DVTMDZ). Other vinyl-containingcompounds useful in the process are vinyltriacetoxysilane andvinyltrialkoxysilanes such as vinyl trimethoxysilane,vinyltriethoxysilane, and vilytriisoproxysilanes.

In one embodiment, the functionalized substrates comprise a combinationof alkyldisilazanes and vinyl-containing disilazanes. The ratio ofalkyldisilazane to vinyl-containing disilazane can be from about 1000:1to about 1:1000. In one embodiment, the ratio of alkyldisilazane tovinyl-containing disilazane can be from about 500:1 to about 1:500. Inanother embodiment, the ratio of alkyldisilazane to vinyl-containingdisilazane can be from about 100:1 to about 1:100. In still anotherembodiment, the ratio of alkyldisilazane to vinyl-containing disilazanecan be from about 10:1 to about 1:10. Here as elsewhere in thespecification and claims, numerical values can be combined to form newand non-disclosed ranges. In one embodiment, the substrates arefunctionalized with both hexamethyldisilazane anddivinyltetramethylsilazane.

Metal Catalyst Material

The metal catalyst compositions comprise a metal-containing polymermatrix material attached to the (functionalized) substrate particles.The metal-containing polymer matrix material can be formed by reactingthe metal-containing polymer matrix material and the substrate underconditions sufficient to bond the polymer matrix material to thefunctional groups on the substrates. In one embodiment, themetal-containing polymer matrix comprises a polyhydrosiloxane comprisingSiH groups, and the SiH groups react with the functional groups disposedon the substrate material. FIG. 1 is a schematic illustrating a scheme10 for forming catalyst materials in accordance with aspects of thepresent invention. As shown in FIG. 1, a polymer material 20(illustrated as PMHS in FIG. 1) is reacted with a metal complex (e.g., aplatinum complex) to provide a metal-containing polymer matrix 30comprising nanoparticles 32 encapsulated in the matrix. Themetal-containing polymer matrix 30 is reacted with a support material 40(e.g., functionalized silica particles) to provide a catalyst material50 comprising the metal-containing polymer matrix bonded to the supportmaterial.

The reaction of the polymer functional moieties with the functionalgroups attached to the substrate can be carried out by any suitablemeans depending on the moieties undergoing reaction. For example, thereaction may be carried out in the presence or absence of a solvent asdesired. In one embodiment the reaction is carried out at a temperatureof from about 5° C. and 150° C. In one embodiment, the reaction iscarried out at a pressure ranging from about 0.001 to about 10 bar.

The metal loading concentration in the metal catalyst material can befrom about 0.001 to about 20 percent by weight based on the total weightof the substrate particles. In one embodiment, the metal loadingconcentration in the metal catalyst material can be from about 0.01 toabout 15 percent by weight based on the total weight of the substrateparticles. In another embodiment, the metal loading concentration in themetal catalyst material may be from about 0.05 to about 5 percent byweight based on the total weight of the substrate particles. In stillanother embodiment, the metal loading concentration in the metalcatalyst material may be from about 0.1 to about 1 percent by weightbased on the total weight of the substrate particles.

The metal catalysts can be employed as catalysts for a wide variety ofreactions including, but not limited to hydrosilylation, hydroxylation,silaesterification, hydrogenation, oxidation, Heck and Suzuki coupling,dehydrocoupling or any other metal catalyzed reaction now known ordeveloped in the future. The present invention is particularly suitablein a hydrosilylation process comprising contacting a silicon hydridewith an unsaturated reactant in the presence of a metal catalyst.Silicon hydrides useful in the present process can be a polymerdescribed by the general formula (1) or a monomer having a generalformula R′_(m)H_(n)SiX_(4-m-n), where each R′ is independently selectedfrom the group consisting of alkyls comprising one to 20 carbon atoms,cycloalkyls comprising four to 12 carbon atoms, and aryls; m=0 to 3, n=1to 3, and m+n=1 to 4. R′ can be a substituted or unsubstituted alkyl,cycloalkyl, or aryl as described. Each X is independently selected fromthe group consisting of OR′ and halides. Examples, of silicon hydridesthat can be useful in the present process include, but are not limitedto, triethoxysilane, trimethoxysilane, trimethylsilane, dimethylsilane,triethylsilane, dichlorosilane, trichlorosilane, methyldichlorosilane,dimethylchlorosilane, ethyldichlorosilane, cyclopentlydichlorosilane,methylphenylchlorosilane and (3,3,3-trifluoropropyl) dichlorosilane. Theunsaturated reactant of the present invention is a hydrocarbon compoundor an unsaturated polyether. The hydrocarbon compound can be describedby, for example, formulas (CH₂═CH(CH₂)_(g))_(h)R′_(i)Si(OR′)_(4-h-i) and(CH₂═CH(CH₂)_(g)R′_(i)SiCl_(4-h-i), where R′ is as previously described,g=0 to 20, h=1 to 3, i=0 to 3, and h+i=1 to 4. The unsaturatedhydrocarbon compounds may also comprise 1-hexene and 1-5 hexadiene,trans-2-hexene, styrene, alpha-methylstyrene, eugenol, 1-octene, allylglycidylether, trivinylcyclohexane, allylmethoxytriglycol,allylmethacrylate, allylamine, trichloroethylene, allyl and vinyl ethersand dichlorostyrene. The unsaturated polyethers of this invention areblocked or random polyoxyalkylenes having the general formula (X), (Y),or (Z):

R¹(OCH₂CH₂)_(z)(OCH₂CH[R³])_(w)OR²  (X);

R²O(CH[R³]CH₂O)_(w)(CH₂CH₂O)_(z)CR⁴ ₂C≡CCR⁴₂(OCH₂CH₂)_(z)(OCH₂CH[R³]_(w)R²  (Y);

or

H₂C═CCH₂[R⁴](OCH₂CH₂)_(z)(OCH₂CH[R³])_(w)CH₂[R⁴]C═CH₂  (Z)

In the formulas, R¹ denotes an unsaturated organic group containing from3 to 10 carbon atoms such as allyl, methallyl, propargyl, or 3-pentynyl.When the unsaturation is olefinic, it is desirably terminal tofacilitate smooth hydrosilylation. However, when the unsaturation is atriple bond it may be internal. R² is hydrogen, or a polyether cappinggroup of from 1 to 8 carbon atoms such as alkyl groups (e.g., CH₃,n-C₄H₉ or i-C₈H₁₇), acyl groups (e.g., CH₃COO—, t-C₄H₉ COO),beta-ketoester group (e.g., CH₃C(O)CH₂C(O)O—), or a trialkylsilyl group.R³ and R⁴ are monovalent hydrocarbon groups such as C₁-C₂₀ alkyl group(e.g., methyl, ethyl, isopropyl, 2-ethylhexyl, dodecyl and stearyl), oraryl groups (e.g., phenyl and naphthyl), or alkaryl groups (e.g.,benzyl, phenylethyl and nonylphenly), or cycloalkyl groups (e.g.,cyclohexyl and cyclooctyl). R⁴ can also be hydrogen. In one embodiment,the R³ and/or R⁴ groups are methyl. The subscript z is 0 to 100inclusive, and w is 0 to 100 inclusive, but z+w>0. In one embodiment,the values of z and w are 1 to 50 inclusive.

The catalysts exhibit excellent activity and can provide high conversionrates in a shorter time period compared to other heterogeneous metalcatalysts. Additionally, the catalysts can be recovered by simplefiltration techniques and reused to catalyze a reaction. In oneembodiment, the catalysts can be reused at least 5 times and exhibitexcellent catalytic activity, even comparable or substantially the sameas the catalytic activity for the first use of the catalyst. In oneembodiment, the catalyst can be used at least 7 times, at least 8 times,even at least 10 times and still exhibit excellent catalytic activity.In one embodiment, the catalytic activity of the catalyst after a first,second, third, fourth, or fifth reuse is substantially similar to thecatalytic activity of the catalyst the first time the catalyst is used.In one embodiment, the catalyst has a catalytic activity the same as orat least 85%, 90%, 95%, 99%, 99.9%, 99.99% or even at least about99.999% of the catalytic activity of the catalyst used to conduct aprior reaction. As used herein the catalytic activity can be evaluatedby or refer to the percent conversion or the rate of reaction for aparticular reaction.

The catalysts of the present invention may be used in a batch, semibatch, or continuous mode at temperatures between −20° C. and 500° C.,−10° C. to about 250° C., about 0° C. to about 200° C., even about 5° C.to about 150° C. The catalysts can be formed at pressures of from about0.001 to about 100 bar, in one embodiment at a pressure from 0.001 barto about 10 bar. A stirred bed reactor may be run under batch,semi-batch and continuous conditions. In contrast, a fixed bed reactoris typically run under continuous conditions.

While the invention has been described with respect to variousembodiments, aspects of the invention may be further understood in viewof the following examples. The examples are for illustrating aspects ofthe invention and are not intended to limit the invention.

EXAMPLES Example 1 Modification of Silica Surface

A mixture of 15 g of silica gel procured from Sigma-Aldrich, 4 g ofHexamethyldisilazane (HMDZ), and 0.2 g of Divinyltetramethyldisilazane(DVTMDZ) are added into a 500 ml round bottom flask. The round bottomflask is equipped with a magnetic stirrer, reflux condenser and athermometer. To the above reactant solution, 4 g of water and 100 g ofisopropyl alcohol (IPA) are added. The temperature of the reaction ismaintained in between 70-80° C. The reaction is continued under stirringfor 4 hours. After cooling, the solution is decanted off and dried at65° C. for 3 hours in a drying oven. This gives a silica powder havinghydrophobic vinyl groups on the silica surface.

Example 2 Synthesis of Uncapped Pt/SiO₂ Catalyst

A mixture of 42 mg of Pt complex (cyclooctadienemethylplatinum(II)(0.012 mmol, 42 mg), polymethylhydrosiloxane (0.182 mmol, 600 mg, Mw3300), and 25 ml toluene solution are added in a 100 ml 3-necked roundbottom flask. Polymethylhydrosiloxane (PMHS) acts as both the reducingand stabilizing agent. The round bottom flask is equipped with amagnetic stirrer, reflux condenser and a thermometer. The flask is incontinuous supply of dry nitrogen gas. The reaction mixture issubsequently heated to 80° C. for 24 hours to form Pt metal atoms fromPt ions via chemical reduction process using the PMHS polymer. After 24hours, the color of the solution changed from white to a dark yellowishcolor, which indicates that colloidal particles of Pt are formed in theprocess. Furthermore, the disappearance of the absorption peak(wavelength=319.0 nm) for metal ions in the UV spectrum also suggeststhat Pt nano metal particles are formed in the solution. Afterconfirming Pt nano-particle formation by UV spectroscopy, nitrogen flowis stopped and flow of oxygen (2 ml/min) is started into the roundbottom flask to promote cross-linking of the PMHS polymer and toencapsulate the Pt nano-particles in a cross-linked PMHS matrix. Thestabilization of Pt nano-particles in a cross-linked PMHS matrix iscontinued for 15 mins. The PMHS stabilized Pt nano-particles (taken outfrom flask) and 7.5 g of vinyl functionalized silica (particle size:100-200 mesh size or 80-100 μm) from example 1 are transferred into apetri dish and mixed thoroughly to form a homogeneous catalyst powder.This catalyst is then further dried in an oven for 3 hrs to remove anyvolatile contents. This gives an uncapped Pt/SiO₂ catalyst powder havinga Pt content of 0.2% by weight.

Example 3 Synthesis of Capped Pt/SiO₂ Catalyst

A mixture of 5 g of uncapped catalyst from Example 2, 1.66 g ofhexamethyldisilazane (HMDZ), and 4 g of water are added into a 250 mlround bottom flask. The round bottom flask is equipped with a magneticstirrer, reflux condenser and a thermometer. To the above reactantsolution 50 g of isopropanol (IPA) is added. The temperature of thereaction is maintained in between 70-80° C. The reaction is continuedunder stirring for 4 hours. After cooling, the solution is decanted offand dried at 65° C. for 3 hours in a drying oven. This gives a cappedPt/SiO₂ catalyst powder having a Pt content of 0.2% by weight.

FIG. 2 a shows a TEM (transmission electron microscopy) image of thecapped Pt/SiO₂ catalyst taken at 135,000 magnification. FIG. 2 b shows aTEM image of the capped Pt/SiO₂ catalyst prepared by a method describedin Example 3 taken at 650,000 magnification. From the image in FIG. 2 b,it is shown that platinum nanoparticles with a size of 1-5 nm areuniformly dispersed in a cross-linked siloxane network on the catalystsurface.

FIG. 3 is a CP/MAS solid state ²⁹Si NMR spectrum of the capped Pt/SiO₂catalyst prepared by a method described in Example 3 and shows thepresence of cross-linked siloxane network (CH₃SiO_(3/2)) andtrimethylsiloxane [(CH₃)₃SiO_(1/2)] moieties onto the silica (SiO₂)support. The presence of these moieties was further documented by FTIRspectroscopy, which showed characteristic signals associated withSi—O—Si and Si—CH₃ bonds. FIG. 4 shows the results of analysis of cappedPt/SiO₂ catalyst by FTIR spectroscopy. As shown in FIG. 4, thedisappearance of Si—H and Si-vinyl groups confirms that the residualSi—H groups of condensed siloxane polymer (contains encapsulated Ptnano-particles) are reacted with vinyl groups of silica surface viahydrosilylation reaction.

Examples 4-16 Reactions Employing Catalyst Compositions

The catalysts of Examples 2 and 3 are utilized in various reactionsdescribed in Examples 4-16.

Example 4

The hydrosilylation of 1-octene and heptamethyltrisiloxane hydride isevaluated in the presence of a 0.2% Pt/SiO₂ catalyst prepared by amethod similar to method for preparing Pt/SiO₂ catalyst described inExample 2. The hydrosilylation experiments are conducted in a 3-neckedround bottom flask. The round bottom flask is equipped with a magneticstirrer, reflux condenser and a thermometer. 1-octene (0.1651 mol, 18.5grams) and heptamethyltrisiloxane hydride (0.1324 mol, 29.4 grams) areadded into the round bottom flask and the temperature is maintained at120° C. The catalyst (20 ppm of Pt metal) is added to the reactionmixture at 120° C., and the moment of this addition is marked as thebeginning of the reaction. Disappearance of starting materials andformation of products are recorded by ¹HNMR. The reaction temperature,reaction time, and conversion of heptamethylhydrosiloxane hydride andyield of the hydrosilylated product are reported in Table 1.

TABLE 1 Reaction Conditions Pt % % Reactants Temp Loading ConversionHydrosilylated Example Olefin SiH (° C.) (ppm) Time of Si—H Product 41-octene Heptamethyltrisiloxane 80-90 20   2 hrs 98 98 hydride 7Allylglycidylether Heptamethyltrisiloxane 120 20 5.5 hrs 30 30 hydride 8Polyalkyleneoxide Heptamethyltrisiloxane 120 20 8.5 hrs 75 75 polymerhydride 9 Eugenol Hydrogen terminated 120 10  12 mins 99 99 polysiloxanehydride 10 Allylmethoxytriglycol Undecamethylpenta 120 20   1 hr 70 70siloxane 11 1-octene Triethoxy silane 120 400   4 hr 8 8

Example 5

The reuse potential of the 0.2% Pt/SiO₂ (synthesized catalyst preparedby a method described in Example 2) in the hydrosilylation of 1-octeneand heptamethyltrisiloxane hydride is evaluated. The experiment isrepeated using the same procedure described in Example 4. After thecompletion of reaction, the catalyst is recovered by simple filtrationand recharged with fresh reactants, and reused in the next reaction.Results of reuse test are reported in Table 2. From Table 2, it is clearthat the synthesized Pt/SiO₂ catalyst can be reused up to five timeswithout any loss of catalytic activity. Table 2 clearly suggests that aminimum amount of Pt (<0.2 ppm) was leached into the product samples.

TABLE 2 Reaction Conditions Pt % Hydro- Leached Temp Loading silylatedPt amount Experiment (° C.) (ppm) Time product (ppm) Use 1 80-90 20 2hrs 98 0.18 Reuse 2 80-90 20 2 hrs 97 0.005 Reuse 5 80-90 20 2 hrs 980.001

Example 6

Evaluation of the hydrosilylation of 1-octene and heptamethyltrisiloxanehydride in the presence of 0.2% Pt/SiO₂ catalyst prepared by a methodsimilar to method for preparing Pt/SiO₂ catalyst described in Example 2except that different mole ratios of the polymethylhydrosiloxane to Ptcomplex ratios are used. The experiment is repeated using the sameprocedure described in Example 4. The mole ratios of PMHS to Pt complex,reaction time and conversion of heptamethylhydrosiloxane hydride andyield of the hydrosilylated product are reported in Table 3. As shown inTable 3, a ratio of PMHS polymer to Pt complex(cyclooctadienedimethylplatinum(II)) of 15:1 illustrates an exemplaryembodiment for achieving both high activity and reduced Pt leaching.

TABLE 3 Mole ratio of % Hydro- Leached PHMS:Pt Reaction % Conversionsilylated Pt amount complex time of Si—H product (ppm) 15:1 2 hrs 98 980.18 10:1 1 hr  98 98 >5  20:.1 3 hrs 80 80 0.18

Example 7

Evaluation of the hydrosilylation of allylglycidylether andheptamethyltrisiloxane hydride in the presence of 0.2% Pt/SiO₂ catalystprepared by a method similar to method for preparing Pt/SiO₂ catalystdescribed in Example 2. The hydrosilylation experiments are conducted ina 3-necked round bottom flask. The round bottom flask is equipped with amagnetic stirrer, reflux condenser and a thermometer. Allylglycidylether(0.04 mol. 10 grams) and heptamethyltrisiloxane hydride (0.075 mol, 16.9grams) are added into the round bottom flask and the temperature ismaintained at 120° C. The catalyst (20 ppm of Pt metal) is added to thereaction mixture at 120° C., and the moment of this addition is markedas the beginning of the reaction. Disappearance of starting materialsand formation of products are recorded by ¹HNMR. The reactiontemperature, reaction time and conversion of heptamethylhydrosiloxanehydride are reported in Table 1.

Example 8

Evaluation of the hydrosilylation of methoxy terminatedallylplyethyleneoxide (Mw˜350) and heptamethyltrisiloxane hydride in thepresence of 0.2% Pt/SiO₂ catalyst prepared by a method similar to methodfor preparing Pt/SiO₂ catalyst described in Example 2. Thehydrosilylation experiments are conducted in a 3-necked round bottomflask. The round bottom flask is equipped with a magnetic stirrer,reflux condenser and a thermometer. Polyalkyleneoxide polymer (0.0571mol, 20 grams) and heptamethyltrisiloxane hydride (0.0304 mol. 15 grams)are added into the round bottom flask and the temperature is maintainedat 120° C. The catalyst (20 ppm of Pt metal) is added to the reactionmixture at 120° C., and the moment of this addition is marked as thebeginning of the reaction. Disappearance of starting materials andformation of products are recorded by ¹HNMR. The reaction temperature,reaction time and conversion of heptamethylhydrosiloxane hydride andyield of the hydrosilylated product are reported in Table 1.

Example 9

Evaluation of the hydrosilylation of eugenol and hydrogen terminatedpolydimethylsiloxane (Average Mw˜3300) in the presence of 0.2% Pt-silicacatalyst prepared by a method similar to a method for preparingsupported catalyst described in Example 2. The hydrosilylationexperiments are conducted in a 3-necked round bottom flask. The roundbottom flask is equipped with a magnetic stirrer, reflux condenser and athermometer. Eugenol (0.0608 mol, 10 grams) and hydrogen terminateddisiloxane (0.0288 mol, 95.177 grams) are added into the round bottomflask and the temperature is maintained at 120° C. The catalyst (10 ppmof Pt metal) is added to the reaction mixture at 120° C., and the momentof this addition is marked as the beginning of the reaction.Disappearance of starting materials and formation of products arerecorded by ¹HNMR. The reaction temperature, reaction time andconversion of hydrogen terminated polydimethylsiloxane and yield of thehydrosilylated product are reported in Table 1.

Example 10

Evaluation of the hydrosilylation of allylmethoxytriglycol andundecamethylpentasiloxane [Me₃SiO(Me₂SiO)₂(MeHSiO)SiMe₃] (as usedherein, “Me” refers to methyl group) in the presence of 0.2% Pt-silicacatalyst prepared by a method similar to a method for preparingsupported catalyst described in Example 2. The hydrosilylationexperiments are conducted in a 3-necked round bottom flask. The roundbottom flask is equipped with a magnetic stirrer, reflux condenser and athermometer. Allylmethoxytriglycol (0.048 mol, 10 grams) andundecamethylpentasiloxane (0.0303 mol, 11.3 grams) are added into theround bottom flask and the temperature is maintained at 120° C. Thecatalyst (20 ppm of Pt metal) is added to the reaction mixture of at120° C., and the moment of this addition is marked as the beginning ofthe reaction. Disappearance of starting materials and formation ofproducts are recorded by ¹HNMR. The reaction temperature, and conversionof undecamethylpentasiloxane and yield of the hydrosilylated product arereported in Table 1.

Example 11

Evaluation of the hydrosilylation of 1-octene and triethoxysilane in thepresence of 0.2% Pt-silica catalyst prepared by a method similar to amethod for preparing supported catalyst described in Example 2. Thehydrosilylation experiments are conducted in a 3-necked round bottomflask. The round bottom flask is equipped with a magnetic stirrer,reflux condenser and a thermometer. 1-octene (0.091 mol, 10.2 grams) andtriethoxysilane (0.078 mol, 12.6 grams) are added into the round bottomflask and the temperature is maintained at 120° C. The catalyst (400 ppmof Pt metal) is added to the reaction mixture at 120° C., and the momentof this addition is marked as the beginning of the reaction.Disappearance of starting materials and formation of products arerecorded by ¹HNMR. The reaction temperature, total conversion oftriethoxysilane and yield of the hydrosilylated product are reported inTable 1.

Example 12

Evaluation of the hydrosilylation of 1-octene and heptamethyltrisiloxanehydride in the presence of 0.2% Pt/SiO₂ catalyst prepared by a methodsimilar to method for preparing Pt/SiO₂ catalyst described in Example 3.The hydrosilylation experiments are conducted in a 3-necked round bottomflask. The round bottom flask is equipped with a magnetic stirrer,reflux condenser and a thermometer. 1-octene (0.1651 mol, 18.5 grams)and heptamethyltrisiloxane hydride (0.1324 mol, 29.4 grams) are addedinto the round bottom flask and the temperature is maintained at 120° C.The catalyst (20 ppm of Pt metal) is added to the reaction mixture at120° C., and the moment of this addition is marked as the beginning ofthe reaction. Disappearance of starting materials and formation ofproducts are recorded by ¹HNMR. The reaction temperature, reaction timeand conversion of heptamethylhydrosiloxane hydride and yield of thehydrosilylated product are reported in Table 4.

Example 13

Evaluation of the hydrosilylation of allylglycidylether andheptamethyltrisiloxane hydride in the presence of 0.2% Pt/SiO₂ catalystprepared by a method similar to method for preparing Pt/SiO₂ catalystdescribed in Example 3. The hydrosilylation experiments are conducted ina 3-necked round bottom flask. The round bottom flask is equipped with amagnetic stirrer, reflux condenser and a thermometer. Allylglycidylether(0.04 mol, 10 grams) and heptamethyltrisiloxane hydride (0.075 mol, 16.9grams) are added into the round bottom flask and the temperature wasmaintained at 120° C. The catalyst (20 ppm of Pt metal) is added to thereaction mixture at 120° C., and the moment of this addition is markedas the beginning of the reaction. Disappearance of starting materialsand formation of products are recorded by ¹HNMR. The reactiontemperature, reaction time, conversion of heptamethylhydrosiloxanehydride and yield of the hydrosilylated product are reported in Table 4.

Example 14

Evaluation of the hydrosilylation of methoxy terminatedallylpolyethyleneoxide (Mw˜350) polymer and heptamethyltrisiloxanehydride in the presence of 0.2% Pt/SiO₂ catalyst prepared by a methodsimilar to method for preparing Pt/SiO₂ catalyst described in Example 3.The hydrosilylation experiments are conducted in a 3-necked round bottomflask. The round bottom flask is equipped with a magnetic stirrer,reflux condenser and a thermometer. Polyalkyleneoxide polymer (0.0571mol, 20 grams) and heptamethyltrisiloxane hydride (0.0304 mol, 10.66grams) were added into the round bottom flask and the temperature ismaintained at 120° C. The catalyst (20 ppm of Pt metal) is added to thereaction mixture of at 120° C., and the moment of this addition ismarked as the beginning of the reaction. Disappearance of startingmaterials and formation of products are recorded by ¹HNMR. The reactiontemperature, reaction time and conversion of heptamethylhydrosiloxanehydride and yield of the hydrosilylated product are reported in Table 4.

Example 15

Evaluation of the hydrosilylation of eugenol and hydrogen terminatedpolydimethylsiloxane (Average Mw ˜3300) in the presence of 0.2%Pt-silica catalyst prepared by a method similar to a method forpreparing supported catalyst described in Example 3. The hydrosilylationexperiments are conducted in a 3-necked round bottom flask. The roundbottom flask is equipped with a magnetic stirrer, reflux condenser and athermometer. Eugenol (0.0608 mol, 10 grams) and hydrogen terminateddisiloxane (0.0288 mol, 95.177 grams) are added into the round bottomflask and the temperature is maintained at 120° C. The catalyst (10 ppmof Pt metal) is added to the reaction mixture at 120° C., and the momentof this addition is marked as the beginning of the reaction.Disappearance of starting materials and formation of products arerecorded by ¹HNMR. The reaction temperature, reaction time andconversion of hydrogen terminated polydimethylsiloxane and yield of thehydrosilylated product are reported in Table 4.

Example 16

Evaluation of the hydrosilylation of 1-octene and triethoxysilane in thepresence of 0.2% Pt-silica catalyst prepared by a method similar to amethod for preparing supported catalyst described in Example 3. Thehydrosilylation experiments are conducted in a 3-necked round bottomflask. The round bottom flask is equipped with a magnetic stirrer,reflux condenser and a thermometer. 1-octene (0.091 mol, 10.2 grams) andtriethoxysilane (0.078 mol, 12.6 grams) are added into the round bottomflask and the temperature is maintained at 120° C. The catalyst (20 ppmof Pt metal) is added to the reaction mixture at 120° C., and the momentof this addition is marked as the beginning of the reaction.Disappearance of starting materials and formation of products arerecorded by ¹HNMR. The reaction temperature, total conversion oftriethoxysilane, and % yield of the hydrosilylated product are reportedin Table 4.

TABLE 4 Reaction Conditions Pt % Reactants Temp Loading Conv. %Hydrosilylated Ex. Olefin SiH (° C.) (ppm) Time of Si—H Product 121-octene HMTS 80-90 20   2 hrs 98 98 13 AGE HMTS hydride 120 20 2.5 hrs98 98 14 PAO HMTS hydride 120 20   1 hr 80 80 polymer 15 EugenolH-terminated 120 10  12 mins 99 99 polydimethyl siloxane 16 1-octeneTriethoxysilane 120 20  45 mins 98 60 AGE = Allylglycidylether PAO =Polyalkyleneoxide HMTS = Heptamethyltrisiloxane

Comparison to Conventional Catalysts

The catalytic activity of a synthesized Pt/SiO₂ catalyst prepared by amethod described in Example 3 is compared with that of a catalyst madewith traditional methods (a 3.6% Pt metal (500 nm) deposited on silicaavailable from JM as 3.6R210, 3.6% platinum on silica catalyst anddesignated as “Commercial” in Table 5) for various hydrosilylationreactions in accordance with Examples 11-15. The results of theexperiment are shown in Table 5.

TABLE 5 % Hydro- Reaction % Conversion silylated Example Catalyst typeTime of Si—H product 11 Example 3 2 hrs 98 98 11 Commercial 6 hrs 55 5512 Example 3 2.5 hrs 98 98 12 Commercial 5.5 hrs 70 70 13 Example 3 1 hr80 80 13 Commercial 4.5 hrs 80 80 14 Example 3 12 mins 99 99 14Commercial 65 mins 72.5 72.5 15 Example 3 45 mins 98 60 15 Commercial4.5 hrs 9 9From Table 5, it is clear that the synthesized Pt/SiO₂ catalystaccording to the present invention exhibits superior catalytic activityin terms of both the rate of conversion and completeness of the reactionthan those of commercial Pt/SiO₂ catalyst.

Product samples obtained with (1) a catalyst in accordance with aspectsof the present invention, (2) a homogenous catalyst, and (3) a supportednano Pt catalyst were visually compared. The material made with thecatalyst in accordance with the present invention is clear (<0.3 ppm ofPt leaching), while the material formed using the other catalysts has ayellowish color (which indicates leaching (>5 ppm) of the platinum intothe solution). This result suggests that the instant method our approachof preparing supported nano Pt catalyst is superior in arresting theleaching compared to the conventional techniques of synthesizing asupported nano Pt catalyst.

Other Applications of the Present Catalyst Example 18 Pt/SiO₂ Catalystfor Hydroxylation of Triethylsilane

Hydroxylation of triethylsilane is carried in the presence of 0.2%Pt-silica catalyst prepared by a method similar to a method forpreparing supported catalyst described in example 3. A 300 ml roundbottom flask is thoroughly flushed with dry nitrogen gas and chargedwith 0.05 g of 0.2% Pt-silica catalyst. To this solid catalyst, drytetrahydrofuran (2 ml), a triethylsilane (1.0 mmol) and H₂O (2.0 mmol)are added consecutively and the reaction mixture is stirred at roomtemperature for 5 hours. The triethylsilanol product is analyzed byHNMR.

Example 19 Pt/SiO₂ Catalyst for Hydrogenation of Acetylene

Hydrogenation of acetylene is carried in the presence of 0.2% Pt-silicacatalyst (synthesized by a method described in example 3) by feeding aninitial gas mixture of 9.8 mol % C₂H₂, 9.5 mol % N₂ and 80.7 mol % H₂ tothe reactor at a flow rate of 1720 ml/min and at atmospheric pressure.Composition of gas streams is measured with gas chromatography, andreported in mol %.

Embodiments of the invention have been described above and, obviously,modifications and alterations will occur to others upon the reading andunderstanding of this specification. The invention and any claims areintended to include all modifications and alterations insofar as theycome within the scope of the claims or the equivalent thereof.

1. A heterogeneous catalyst comprising a metal-containing polymer matrixcovalently bonded to a support material wherein the metal-containingpolymer matrix comprises metal nanoparticles encapsulated in a polymermatrix chosen from an organic polymer matrix or a siloxane polymermatrix.
 2. (canceled)
 3. The catalyst of claim 1, wherein the polymermatrix comprises an organic polymer matrix comprising a polymer orcopolymer of a vinyl aromatic, a vinyl halide, an alpha monoolefin, anacrylonitrile, an acrylate, an amide, an acrylamide, an ester, or acombination of two or more thereof.
 4. The catalyst of claim 1, whereinthe polymer matrix is derived from a silicon hydride-containingpolyorganohydrosiloxane of the general formula:M¹ _(a)M² _(b)D¹ _(c)D² _(d)T¹ _(e)T² _(f)Q_(j) wherein:M¹=R¹R²R³SiO_(1/2); M²=R⁴R⁵R⁶SiO_(1/2); D¹=R⁷R⁸SiO_(2/2);D²=R⁹R¹⁰SiO_(2/2); T¹=R¹¹SiO_(3/2); T²=R¹²SiO_(3/2); Q=SiO_(4/2); R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are aliphatic,aromatic or fluoro monovalent hydrocarbon having from 1 to 60 carbonatoms; at least one of R⁴, R⁹, R¹² is hydrogen; and the subscript a, b,c, d, e, f, and j are zero or positive subject to the followinglimitations: 2≦a+b+c+d+e+f+j≦6000, and b+d+f>0.
 5. The catalyst of claim1, wherein the polymer matrix comprises a functional group chosen from ahydride; a carboxyl group, an alkoxy functional group, an epoxyfunctional group, a triaz-1-yn-2-ium functional group, an anhydridegroup, a mercapto group, an acrylate, an alkyl, an olefinic, a dienyl,or a combination of two or more thereof.
 6. The catalyst of claim 1,wherein the polymer matrix comprises a functional group chosen from—S_(i)—H; —Si(CH₂)_(n)COOR¹³, —Si(CH₂)nSi(OR¹⁴)₃, —Si(OR¹⁵)₁₋₃,—Si(CH₂)_(n)-epoxy, —Si—(CH₂)_(n)—N—N≡N, etc. where R¹³, R¹⁴, and R¹⁵ ischosen from hydrogen, hydrocarbyl, substituted hydrocarbyl, or acombination of two or more thereof, and n is chosen from 1 to
 26. 7. Thecatalyst of claim 1, wherein the polymer matrix comprises a polysiloxaneformed from a hydrosiloxane and a vinyl silicon compound.
 8. (canceled)9. The catalyst of claim 1, wherein the metal nanoparticles are chosenfrom nanoparticles of aluminum, iron, silver, zinc, gold, copper,cobalt, nickel, platinum, manganese, rhodium, ruthenium, palladium,titanium, vanadium, chromium, molybdenum, cadmium, mercury, calcium,zirconium, iridium, cerium, oxides and sulfides of such metal, orcombinations of two or more thereof.
 10. The catalyst of claim 1 whereinthe metal-containing polymer matrix has a ratio of polymer to metal offrom about 1:1000 to about 100:1.
 11. The catalyst of claim 1, whereinthe metal-containing polymer matrix has a ratio of polymer to metal offrom about 1:1 to about 20:1.
 12. The catalyst of claim 1, wherein themetal-containing polymer matrix has a ratio of polymer to metal of fromabout 10:1 to about 20:1.
 13. The catalyst of claim 1, wherein themetal-containing polymer matrix has a ratio of polymer to metal of fromabout 12:1 to about 16:1.
 14. The catalyst of claim 1-13 wherein themetal particles have a particle size of from about 1 to about 100nanometers.
 15. The catalyst of claim 1 wherein the support material ischosen from silicon, a silicate such as a sodium silicate, aborosilicate, or a calcium aluminum silicates, clay, silicate, silica,starch, carbon, alumina, titania, calcium carbonate, barium carbonate,zirconia, metal oxide, carbon nanotubes, synthetic and natural zeolites,polymeric resins in bead or fibrous form, or and mixtures of two or morethereof.
 16. (canceled)
 17. The catalyst of claim 1 wherein the metalloading ranges from about 0.05 to about 5 percent by weight of thesupport material.
 18. The catalyst of claim 1 wherein the metal loadingranges from about 0.1 to about 1 percent by weight of the supportmaterial.
 19. The catalyst of claim 1, wherein the support materialcomprises a functional group chosen from a group such as silanol,alkoxy, acetoxy, silazane, oximino-functional silyl group, hydroxyl,acyloxy, ketoximino, amine, aminoxy, alkylamide, hydrogen, allyl, analiphatic olefinic group, aryl, hydrosulfide, or a combination of two ormore thereof.
 20. The catalyst of claim 1, wherein the support materialcomprises a functional group chosen from —Si—CH═CH₂, —Si—OH,—Si—(CH₂)_(n)C≡CH, —Si—(CH₂)_(n)—NH₂, —Si—(CH₂)_(n)—OH,—Si—(CH₂)_(n)—SH, or a combination of two or more thereof, and n is1-26.
 21. The catalyst of claim 1 wherein the metal-containing polymermatrix is covalently bonded to the support material via a hydrophobicfunctional group attached to the support material.
 22. The catalyst ofclaim 21 wherein the hydrophobic group is chosen from analkyldisilazane, a vinyl-containing silazane, or a combination thereof.23. A method of synthesizing supported nanoparticle catalysts, themethod comprising: (a) forming a metal-containing polymer matrixcomprising metal nanoparticles encapsulated in a polymer matrix; and (b)attaching the metal-containing polymer matrix to a support material viacovalent chemical bonds.
 24. The method of claim 23 wherein forming themetal-containing polymer matrix comprises forming a colloidal suspensionof metal nano-particles by reacting metal complexes with a siliconhydride-containing polyorganohydrosiloxane solution in suitable solventunder nitrogen atmosphere, and encapsulating the metal nano-particles ina siloxane matrix.
 25. The method of claim 24, wherein the metal complexis selected from a metal salt chosen from PtCl₂, H₂PtCl₆, Pt₂(dba)₃,Pt₂(dvs)₃, Pt(OAc)₂Pt(acac)₂, Na₂PtCl₆, K₂PtCl₆, platinum carbonate,platinum nitrate, 1,5-cycooctadienedimethylplatinum(II), platinumperchlorate, amine complexes of the platinum ammoniumhexachloropalladate(IV), palladium(II) chloride, AuCl₃, Au₂O₃, NaAuO₂,AgCl, AgNO₃, CuSO₄, CuO, Cu(NO₃)₂, CuCl₂, Ru₂O₃, RuCl₂, FeCl₂.6H₂O,ZnCl₂, CoCl₂.6H₂O, NiCl₂.6H₂O, MnCl₂.4H₂O, TiCl₄, vanadium chloride,cadmium chloride, calcium chloride, zirconium tetrachloride, mercuricchloride complexes, or a combination of two or more thereof.
 26. Themethod of claim 24, wherein the silicon hydride-containingpolyorganohydrosiloxane is of the general formula:M¹ _(a)M² _(b)D¹ _(c)D² _(d)T¹ _(e)T² _(f)Q_(j) wherein:M¹=R¹R²R³SiO_(1/2); M²=R⁴R⁵R⁶SiO_(1/2); D¹=R⁷R⁸SiO_(2/2);D²=R⁹R¹⁰SiO_(2/2); T¹=R¹¹SiO_(3/2); T²=R¹²SiO_(3/2); Q=SiO_(4/2); R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are aliphatic,aromatic or fluoro monovalent hydrocarbon having from 1 to 60 carbonatoms; at least one of R⁴, R⁹, R¹² is hydrogen; and the subscript a, b,c, d, e, f, and j are zero or positive subject to the followinglimitations: 2≦a+b+c+d+e+f+j≦6000, and b+d+f>0.
 27. The method of claim24, wherein encapsulating the metal nano-particles in the siloxanematrix comprises exposing the colloidal suspension to the presence ofoxygen for a time period of from about 10 to about 30 minutes.
 28. Themethod of claim 24 further comprising an optional step of removing atleast about 50% of the solvent from the colloidal solution.
 29. Themethod claim 23, wherein the ratio of polymer to metal complex rangesfrom about 0.001 to about
 100. 30. The method of claim 23, wherein themolecular weight of the polysiloxanes range from 100 to 50000, and theSi—H content of the polysiloxanes ranges from 0.001 to 99 mole percent.31. The method claim 23, wherein the nanoparticles are chosen from atleast one of aluminum, iron, silver, zinc, gold, copper, cobalt, nickel,platinum, manganese, rhodium, ruthenium, palladium, titanium, vanadium,chromium, molybdenum, cadmium, mercury, calcium, zirconium, iridium,cerium, oxides and sulfides thereof.
 32. The method of any of claims23-31, wherein the polymer matrix comprises a functional group chosenfrom a hydride; a carboxyl group, an alkoxy functional group, an epoxyfunctional group, a triaz-1-yn-2-ium functional group, an anhydridegroup, a mercapto group, an acrylate, an alkyl, or a combination of twoor more thereof.
 33. The method of claim 23, wherein the polymer matrixcomprises a functional group chosen from —S_(i)—H; —Si(CH₂)_(n)COOR¹³,—Si(CH₂)nSi(OR¹⁴)₃, —Si(OR¹⁵)₁₋₃, —S_(i)(CH₂)_(n)-epoxy,—Si—(CH₂)_(n)—N—N≡N, etc. where R¹³, R¹⁴, and R¹⁵ is chosen fromhydrogen, hydrocarbyl, substituted hydrocarbyl, or a combination of twoor more thereof, and n is chosen from 1 to
 26. 34. The method of claim23, wherein the support material is chosen from silicon, a silicate suchas sodium silicate, a borosilicate, or a calcium aluminum silicate,clay, silica, starch, carbon, alumina, titania, calcium carbonate,barium carbonate, zirconia, metal oxide, carbon nanotubes, synthetic andnatural zeolites, polymeric resins in bead or fibrous form, or a mixtureof two or more thereof.
 35. The method of claim 23, where in thereaction is carried out at a temperature between about 5 degree C. toabout 150 degree C., and at a pressure ranging from 0.001 bar to 10 bar.36. The method of claim 23, wherein said nanoparticles have a size inthe range of from about 1 to about 100 nanometers.
 37. The method ofclaim 23, wherein the reaction is carried out in the presence or absenceof suitable solvents.
 38. The method claim 23, further comprising dryingthe supported nanoparticle catalysts
 39. The method of claim 23, whereinsaid support material comprises particles having a size in the rangefrom 50 to 1000 micrometers.
 40. The method of claim 23, wherein theratio of metal loading to support material ranges from about 0.001 to 20percent by weight.
 41. The method of claim 23, wherein the supportmaterial comprises a functional group chosen from a group such assilanol, alkoxy, acetoxy, silazane, oximino-functional silyl group,hydroxyl, acyloxy, ketoximino, amine, aminoxy, alkylamide, hydrogen,allyl, an aliphatic olefinic group, aryl, hydrosulfide, or a combinationof two or more thereof.
 42. The method claim 23 wherein the supportmaterial comprises a functional group chosen from —Si—CH═CH₂, —Si—OH,—Si—(CH₂)_(n)C≡CH, —Si—(CH₂)_(n)—NH₂, —Si—(CH₂)_(n)—OH,—Si—(CH₂)_(n)—SH, or a combination of two or more thereof, and n is1-26.
 43. The method of claim 23, wherein the support material isfunctionalized with a hydrophobic group chosen from an alkyldisilazane,a vinyl-containing silazane, trimethyl disilazane, tetramethyldisilazane, pentamethyl disilazane, hexamethyl disilazane, octamethyltrisilazane, hexamethylcyclo trisilazane, tetraethyltetramethylcyclotetrasilazane, tetraphenyldimethyl disilazane, dipropyltetramethyldisilazane, dibutyltetramethyl disilazance, dihexyltetramethyldisilazane, dioctyltetramethyl disilazane, diphenyltetramethyldisilazane, octamethylcyclo tetrasilazane, vinyltriacetoxysilane andvinyltrialkoxysilanes, or a combination of two or more thereof. 44.(canceled)
 45. A metal catalyzed reaction employing a catalyst of claim1, wherein the reaction is chosen preferably from a hydrosilylationreaction, a hydroxylation reaction, a silaesterification reaction, ahydrogenation reaction, a oxidation reaction, a Heck and Suzuki couplingreaction, a dehydrocoupling reaction.
 46. (canceled)
 47. A processcomprising: (a) conducting a metal catalyzed reaction with a catalystcomprising a metal-containing polymer matrix covalently bonded to asupport material; (b) recovering the catalyst; and (c) conducting asubsequent metal catalyzed reaction with the recovered catalyst.
 48. Theprocess of claim 47, wherein the metal catalyzed reaction is chosen fromhydrosilylation, hydroxylation, silaesterification, hydrogenation,oxidation, Heck and Suzuki coupling, dehydrocoupling.
 49. (canceled) 50.A process according to claim 47, wherein, in a hydrosilylation reactioncomprising the reaction of a silicon hydride and an unsaturatedreactant, the silicon hydride is selected from a group described by (a)the formulaM¹ _(a)M² _(b)D¹ _(c)D² _(d)T¹ _(e)T² _(f)Q_(j) wherein:M¹=R¹R²R³SiO_(1/2); M²=R⁴R⁵R⁶SiO_(1/2); D¹=R⁷R⁸SiO_(2/2);D²=R⁹R¹⁰SiO_(2/2); T¹=R¹¹SiO_(3/2); T²=R¹²SiO_(3/2); Q=SiO_(4/2); R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are aliphatic,aromatic or fluoro monovalent hydrocarbon having from 1 to 60 carbonatoms; at least one of R⁴, R⁹, R¹² is hydrogen; and the subscript a, b,c, d, e, f, and j are zero or positive subject to the followinglimitations: 2≦a+b+c+d+e+f+j≦6000, and b+d+f>0, or (b) a monomer havinga general formula R′_(m)H_(n)SiX_(4-m-n), where each R′ is independentlyselected from the group consisting of alkyls comprising one to 20 carbonatoms, cycloalkyls comprising four to 12 carbon atoms, and aryls; m=0 to3, n=1 to 3, and m+n=1 to 4; each X is independently selected from a OR′group or a halide.
 51. The process of claim 50, wherein the siliconhydride is chosen from trimethylsilane, dimethylsilane, triethylsilane,dichlorosilane, trichlorosilane, methyldichlorosilane,dimethylchlorosilane, ethyldichlorosilane, cyclopentlydichlorosilane,methylphenylchlorosilane, (3,3,3-trifluoropropyl),heptamethyltrisiloxane hydride, triethoxysilane, trimethoxysilane,hydrogen terminated polydimethylsiloxane, monochlorosilane, or acombination of two or more thereof.
 52. A process according to claim 50,wherein the unsaturated reactant is selected from the group consistingof a hydrocarbon compound or an unsaturated polyether.
 53. The processof claim 52, wherein the hydrocarbon compound is described by one ormore of the formulas (CH₂═CH(CH₂)_(g))_(h)R′_(i)Si(OR′)_(4-h-i) and(CH₂═CH(CH₂)_(g)R′_(i)SiCl_(4-h-i), where R′ is independently selectedfrom the group consisting of alkyls comprising one to 20 carbon atoms,cycloalkyls comprising four to 12 carbon atoms, and aryls; g is 0 to 20,h is 1 to 3, I is 0-3, and h+i is 1 to
 4. 54. The process of claim 52,where the hydrocarbon compounds is chosen from 1-hexene and 1-5hexadiene, trans-2hexene, styrene, allylmethoxytriglycol,alpha-methylstyrene, eugenol, 1-octene, allyl glycidylether,trivinylcyclohexane, allylmethacrylate, allylamine, trichloroethylene,allyl and vinyl ethers, dichlorostyrene, or a combination of two or morethereof.
 55. The process of claim 52, wherein the unsaturated polyetheris chosen from a blocked or random polyoxyalkylenes having at least oneof the general formulas:R¹(OCH₂CH₂)_(z)(OCH₂CH[R³])_(w)OR²  (X);R²O(CH[R³]CH₂O)_(w)(CH₂CH₂O)_(z)CR⁴ ₂C≡CCR⁴ ₂(OCH₂CH₂)_(z)(OCH₂CH[R³])wR²(Y); orH₂C═CCH₂[R⁴](OCH₂CH₂)_(z)(OCH₂CH[R³])_(w)CH₂[R⁴]C═CH₂  (Z) where R¹denotes an unsaturated organic group containing from 3 to 10 carbonatoms; R² is hydrogen, or a polyether capping group of from 1 to 8carbon atoms chosen from an alkyl group, an acyl group, or atrialkylsilyl group; R³ and R⁴ are monovalent hydrocarbon groups chosenfrom a C₁-C₂₀ alkyl group, an aryl group, an alkaryl group, or acycloalkyl group; R⁴ can also be hydrogen; z is 0 to 100 inclusive and wis 0 to 100 inclusive, with the proviso that z+w>0.
 56. The process ofclaim 47, comprising repeating steps (b) and (c) two or more times. 57.(canceled)
 58. The process of claim 47 wherein the recovered catalysthas a catalytic activity substantially similar to activity of thecatalyst in step (a).
 59. The process of claim 47, wherein the recoveredcatalyst has a catalytic activity that is at least 85% of the catalyticactivity of the catalyst in step (a).
 60. The process of claim 47,wherein the recovered catalyst has a catalytic activity that is at least95% of the catalytic activity of the catalyst in step (a).
 61. Theprocess of claim 47, wherein the recovered catalyst has a catalyticactivity that is at least 99% of the catalytic activity of the catalystin step (a).
 62. The process according to claim 47, wherein the reactionis carried out in a batch, semi batch, or continuous mode at atemperature between about 0 degree C. to 500 degree C. and a pressureranging from 0.01 bar to 100 bar.
 63. The process of claim 47, whereinrecovering the catalyst is accomplished by filtration.
 64. The catalystof claim 1, wherein the support material comprises particle having asize in the range of 50 to 1000 micrometers.